WO2007043688A1 - Element fonctionnel en alliage a base de co et procede de production de cet alliage - Google Patents

Element fonctionnel en alliage a base de co et procede de production de cet alliage Download PDF

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WO2007043688A1
WO2007043688A1 PCT/JP2006/320689 JP2006320689W WO2007043688A1 WO 2007043688 A1 WO2007043688 A1 WO 2007043688A1 JP 2006320689 W JP2006320689 W JP 2006320689W WO 2007043688 A1 WO2007043688 A1 WO 2007043688A1
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phase
type
porous
based alloy
lamellar structure
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PCT/JP2006/320689
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English (en)
Japanese (ja)
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WO2007043688A9 (fr
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Kiyohito Ishida
Kiyoshi Yamauchi
Ryosuke Kainuma
Yuji Sutou
Toshihiro Omori
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Japan Science And Technology Agency
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Priority to EP06821898A priority Critical patent/EP1935997B1/fr
Priority to JP2007540225A priority patent/JP5144270B2/ja
Publication of WO2007043688A1 publication Critical patent/WO2007043688A1/fr
Publication of WO2007043688A9 publication Critical patent/WO2007043688A9/fr
Priority to US12/098,771 priority patent/US8021499B2/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/28—Acidic compositions for etching iron group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/16—Polishing
    • C25F3/22—Polishing of heavy metals

Definitions

  • the present invention relates to a functional member made of a Co base alloy having a porous surface layer capable of imparting various functions, and a method for producing the same.
  • Co-base alloys have excellent corrosion resistance and mechanical strength, so they are used in a wide range of applications such as medical devices, biomaterials, and wear-resistant materials.
  • Cr, Ni, Fe, Mo, C, etc. are added to further improve the properties such as corrosion resistance, oxidation resistance, ⁇ phase stabilization, material strengthening, etc., and various solutions such as solid solution strengthening, precipitation strengthening, work hardening, etc.
  • a strengthening method has been proposed.
  • the present inventors also introduced Cu-Mn-Al-Ni alloys with a lamellar structure in Reference 3, and the lamellar organization of a Co-Al binary alloy is also described in Reference 4. It has been reported.
  • Co-Al alloys have a lamellar structure in which a soft ⁇ -phase and a hard ⁇ -phase are repeated in a minute gap, so they are used as a material for equipment that maintains the required strength even when the wire is thinned and miniaturized.
  • the present inventors have studied various methods for further enhancing the functionality while utilizing the excellent characteristics of the Co-based alloy having a lamellar structure. As a result, it was clarified that the surface layer of the Co-based alloy is made porous by selectively removing either the ⁇ phase or ⁇ phase composing the lamellar structure.
  • the present invention is based on such knowledge, and by selectively removing the ⁇ phase or ⁇ phase from the lamellar structure on the surface of the Co-based alloy, it is modified into a porous surface layer capable of providing various functions.
  • An object of the present invention is to provide a functional member made of a Co-based alloy.
  • the functional member made of the Co-based alloy of the present invention is based on a Co-based alloy having a lamellar structure in which Al: 3 to 15 mass% is included and the ⁇ phase of the fcc structure and the ⁇ phase of ⁇ 2 type overlap each other in layers.
  • the base material surface is modified to a porous structure by selectively removing either the ⁇ phase or ⁇ phase.
  • the content of the alloy component is simply%, and the other percentages are expressed as volume%, area%, and the like.
  • Co-Al binary alloys precipitate as a lamellar structure in which the ⁇ phase of the f.c.c. structure and the ⁇ -type ⁇ phase overlap each other in layers during the solidification process or aging treatment after solution treatment.
  • this composition is based on a binary system of Co-Al, a third component may be added if necessary.
  • the third component one or more of Table 1 are used.
  • the third component is added in a total amount of 0.001 to 60%, or one or more of them are added.
  • Table 1 shows the relationship between the first component that can be added, the amount added, and the precipitate.
  • L12 type ⁇ 'phase, D019 type precipitate, M23C6 type carbide, etc. are formed in the ⁇ phase.
  • Lamella is organized. Selectively remove Ll 2 type ⁇ 'phase, D0i9 type precipitate, M23C6 type carbide, etc., or conversely remove ⁇ phase selectively to remove Ll 2 type ⁇ ' phase, D019 type precipitate, M23C6 type
  • a porous structure derived from the lamellar structure is formed on the surface of the Co-based alloy.
  • the Ll 2 type ⁇ 'phase, D0i9 type precipitates, M23C6 type carbide, etc. will be described as being representative of the ⁇ phase as appropriate.
  • a lamellar structure is generated in the process of solidifying a Co-based alloy that has been prepared and melted to a predetermined composition.
  • solidification methods using unidirectional solidification and melt growth equipment such as the Bridgman furnace can also be used.
  • One organization is obtained.
  • the surface layer of the Co-based alloy is modified into a porous structure in which the cell skeleton is formed.
  • physical polishing, chemical polishing, electrochemical polishing, etc. may be used alone or in combination.
  • Fig. 1 shows a Co-Al binary phase diagram for explaining the mechanism of lamellar structure formation.
  • Fig. 2 shows a SElVi image showing that the lamellar structure produced by a Co-Al binary alloy is made porous by electropolishing.
  • BEST MODE FOR CARRYING OUT THE INVENTION In order to form a lamellar structure similar to the pearlite structure of steel, various elements were mixed with Co, and the relationship between the additive element and the structure was investigated. As a result, alloy components whose solid solubility limit is large in the high temperature range and narrow in the low temperature range are effective for the formation of a lamellar structure so that discontinuous precipitates are formed, and A1 is effective for a lamellar structure. It was found to be an element.
  • the ⁇ phase has a crystal structure of fcc face-centered cubic), and as can be seen from the Co-Al binary phase diagram, it is a phase in which A1 is dissolved in Co and martensite transforms to the hcp structure at low temperature. Sometimes.
  • the ⁇ phase that equilibrates with the ⁇ phase in the Co-Al binary system has a ⁇ 2 type crystal structure, but in the system with the appropriate amount of the third component added, the Ll 2 type ⁇ 'phase, the D0i9 type phase, M 23 C 6 carbide and the like also precipitate.
  • Various precipitates can be identified by X-ray diffraction, TEM observation, etc.
  • a lamellar structure is a multiphase structure in which the ⁇ phase and the crystallized phase or precipitated phase overlap each other, and the finer the layer spacing (lamellar interval) between the ⁇ phase and the crystallized phase or precipitated phase, the better the toughness. Indicates.
  • the lamellar structure is formed by discontinuous precipitation represented by ⁇ ′ ⁇ ⁇ + ⁇ .
  • the ⁇ 'and ⁇ phases are the same, but there is a concentration gap at the interface and the solute concentration in the parent phase does not change.
  • heat treatment is performed in the ⁇ single-phase region, and then the prescribed ⁇ + ⁇ two-phase Discontinuous precipitation occurs when heat treatment is performed in the region.
  • the two phases grow from a grain boundary as a group called a colony, and form a lamellar structure in which the phase and ⁇ phase overlap each other in layers.
  • the Co-Al binary phase diagram (Fig. 1) shows that the solid solubility of the ⁇ phase is greatly reduced below the magnetic transformation temperature.
  • the solid solubility of the ⁇ phase changes drastically at the magnetic transformation temperature, and the difference in solid solubility increases between the high temperature and low temperature regions, causing the driving force for precipitation to increase. It becomes.
  • a lamellar structure can be sufficiently formed by heat treatment at a low temperature.
  • a lamellar structure is also generated by a eutectic reaction.
  • the eutectic reaction is expressed as L ⁇ ⁇ + ⁇ .
  • the eutectic reaction occurs when an alloy containing about 10% A1 is solidified.
  • ⁇ phase and ⁇ phase are crystallized simultaneously, solute atoms diffuse throughout the solidified surface, and two adjacent phases grow at the same time, so that a lamellar structure or a rod-like structure is formed.
  • the volume fractions of both phases are almost equal, a lamellar structure is formed, and when there is a large difference in volume fraction, there is a tendency to form a rod-like structure.
  • For eutectic Co-Al alloys there is a large difference in the volume fraction of ⁇ and ⁇ phases in the high temperature region where the metallographic structure is formed. A lamellar structure is formed because there is not.
  • lamellar structures are formed by eutectoid reactions and continuous precipitation in systems containing the third component. Normal continuous precipitation does not give a lamellar structure, but it tends to become a lamellar structure when a directional precipitation reaction proceeds.
  • the lamellar structure is a structure in which the ⁇ and ⁇ phases are periodically repeated.
  • the lamellar structure formed in the solidification process is a eutectic reaction, and the lamellar structure formed by the aging treatment is a non-reachable precipitation and eutectoid transformation. Etc. Even in continuous deposition, lamellar structures are more likely to be formed by promoting directional deposition.
  • Layer spacing Co-based alloys having a lamellar structure of ⁇ or less have high mechanical strength and a high surface area increase rate after being made porous.
  • the layer spacing that governs the pore size can be controlled by the cooling and aging conditions of the solidification process.
  • the pore size basically depends on the lamellar structure layer spacing, but can be adjusted to a range of 10 nm to ⁇ depending on the lamellar structure.
  • the layer spacing of the lamellar structure can be narrowed and thus a porous surface layer region having a small pore size can be formed.
  • a Co-based alloy having a lamellar structure is physically, chemically or electrochemically polished and either ⁇ phase or ⁇ phase is selectively removed, a porous layer maintaining the lamellar structure skeleton is formed on the surface layer. .
  • the selective removal of the ⁇ and ⁇ phases utilizes the physical differences between the two phases.
  • the relatively soft and chemically noble ⁇ phase is removed by a physical method, and the relatively hard and chemically poor ⁇ phase Tends to be removed by chemical or electrochemical techniques.
  • the surface area of the porous surface layer formed by selective removal of the ⁇ phase or ⁇ phase has a significantly increased surface area compared to the original substrate surface, and the ⁇ phase or ⁇ phase remaining after polishing is three-dimensional. It has a complicated micropore.
  • Such a unique porous structure allows the penetration of drugs, body tissues, lubricants, etc. into the surface of the material, substance retention, sustained release, strong binding, biocompatibility, heat dissipation, catalytic activity, etc. Is added to the Co-based alloy.
  • the Co-based alloy used for the substrate is based on A1: 3-15% Co-Al binary system.
  • A1 is an essential component for the formation of a crystallization phase and a precipitation phase, and the target ⁇ ( ⁇ 2) phase is 3% or more. Generation is ensured. However, if an excess amount of A1 exceeding 15% is included, the matrix becomes ⁇ -phase, and the ratio of lamellar texture with cyclic repetition of ⁇ -phase and ⁇ -phase is significantly reduced.
  • the A1 content is selected in the range of 4 to 10%.
  • Ni, Fe, and Mn are effective components for stabilizing the ⁇ phase and contribute to the improvement of ductility. However, excessive addition adversely affects the formation of lamellar texture.
  • Ni, Fe, and Mn Ni: 01 to 50% (preferably 5 to 40%), Fe: 0.01 to 40% (preferably 2 to 30%), Mn: 0.01 to 30% Each content is determined within the range of (preferably 2 to 20%).
  • Cr, Mo, and Si are effective components for improving corrosion resistance, but excessive addition causes a significant deterioration in ductility.
  • Cr, Mo, Si, Cr 0.01-40% (preferably 5-30%)
  • Si: 01 01-5% Preferably, the content is selected in the range of 1 to 3%.
  • W, Zr, Ta, and Hf are effective components for improving the strength, but excessive addition causes a significant deterioration in ductility.
  • W, Zr, Ta, and Hf are added, W: 0.01 to 30% (preferably 1 to 20%), Zr: 0 01 to 10% (preferably 0.1 to 2%), Ta: 0.01 to : 15% (preferably 0.1 to 10%), Hf: 0.01 to 10% (preferably 0.;! To 2%).
  • Ga, V, Ti, b, and C have the effect of promoting the formation of precipitates and crystallized materials, but when added excessively, the occupancy ratio of the lamellar structure to the entire metal structure tends to decrease.
  • Ga 0.01 to 20% (preferably 5 to: 15%)
  • V 0.01 to 20% (preferably 0.:! To 15%).
  • Ti 0.01 to: L2% (preferably , 0.1 to 10%)
  • Nb 0.01 to 20% (preferably 0.1 to 7%)
  • C 0.001 to 3% (preferably 0.05 to 2%) .
  • Rh, Pd, Ir, Pt, and Au are effective components for improving X-ray contrast, corrosion resistance, and oxidation resistance. However, excessive addition tends to suppress the formation of lamellar tissue.
  • Rh 0.01 to 20% (preferably 1 to: 15%)
  • Pd 0.01 to 20% (preferably 1 to: 15%)
  • Ir 0.01 to 20% (preferably 1 ⁇ : 15%)
  • Pt 0.01-20% (preferably 1-15%)
  • Au 0.01-; 10% (preferably 1-5%).
  • B is an effective component for grain refinement, but if an excessive amount of B is included, the ductility decreases significantly. In the case of addition, in the range of 0 001 to 1% (preferably 0.005 to 0.1%) Select B content.
  • P is an effective component for deoxidation, but if an excessive amount of P is contained, the ductility is significantly reduced.
  • P When added, in the range of 0.001 ⁇ : 1% (preferably 0.01 ⁇ 05%)? Select the content.
  • the ⁇ phase and ⁇ ( ⁇ 2) phase of the fccc structure crystallize while forming a lamellar structure during solidification. Since the lamella interval is proportional to ⁇ _1 / 2 when the growth rate is V, the growth rate V and thus the lamellar interval can be controlled by the cooling rate. Specifically, the faster the cooling rate, the larger the growth rate V and the smaller the lamellar spacing. At slow cooling rates, crystal growth proceeds and the layer spacing increases. Although sufficiently satisfactory properties can be obtained even with forged materials, it is possible to improve the properties by hot working, cold working, strain relief annealing, and the like. Forged materials are forged and hot-rolled as needed, and then formed into target-size plates, wires, pipes, etc. by cold working and drawing.
  • the volume of the lamellar structure in the entire metal structure is 30 volumes. /. By doing so, properties such as high strength and toughness derived from the lamellar structure are imparted.
  • the characteristics of the lamellar structure can be utilized by setting the phase interval between the ⁇ phase and ⁇ ( ⁇ 2) phase of the fcc structure to ⁇ or less. Effective above. When the phase spacing exceeds ⁇ , the characteristics of the lamellar structure, and thus the characteristics of the porous surface layer, cannot be fully exhibited.
  • the melted Co-base alloy is crystallized by forming a lamellar structure in which the ⁇ and ⁇ ( ⁇ 2) phases of the f.c.c. structure overlap each other.
  • the forged material can provide satisfactory characteristics, but the properties can be improved by performing hot working, cold working, strain relief annealing, etc. after forging.
  • a lamellar structure When a lamellar structure is formed by heat treatment, it undergoes solution treatment and aging treatment steps.
  • the cold-worked Co-base alloy When the cold-worked Co-base alloy is solution-treated at a temperature of 900 to 140 CTC, the strain introduced in the process up to the cold treatment is removed, and the precipitate is dissolved in the matrix and the material is homogenized. Is done. Since it is necessary to set the solution temperature sufficiently higher than the recrystallization temperature, it is selected in the range of 900 ° C. or higher and melting point (1400 ° C.) or lower (preferably 1000 to L300 ° C.).
  • the aging temperature is selected in the range of 500 to 900 ° C (preferably 550 to 750 ° C).
  • the interlaminar spacing becomes finer and the volume fraction of precipitates including the ⁇ ( ⁇ 2) phase increases. Finer layer spacing can also be achieved by shortening the aging time.
  • the heating conditions are controlled so that the ratio of the lamellar structure in the entire metal structure is 30% by volume or more, resulting in high strength and high strength derived from the lamellar structure. Properties such as toughness are imparted.
  • the phase interval between the ⁇ phase and ⁇ ( ⁇ 2) phase of the f.c.c. structure is ⁇ or less, the characteristics resulting from the lamellar structure can be used effectively.
  • Co-based alloy with lamellar structure is used for various applications by utilizing its excellent mechanical properties.
  • the surface layer region is made porous by selectively removing either the ⁇ phase or the ⁇ phase constituting one lamella structure.
  • the skeleton of the lamellar structure is maintained, and the traces of the ⁇ phase or ⁇ phase that are selectively removed are micropores. Since the pore size is determined according to the lamellar structure, the ⁇ ( ⁇ 2) phase precipitation state and layer spacing must be controlled by solidification cooling conditions and heat treatment conditions so that a pore size suitable for the application of the functional material made of Co-based alloy can be obtained. Is preferred.
  • ⁇ phase or ⁇ phase is selectively removed by immersing a Co-based alloy having a lamellar structure in a polishing solution.
  • the polishing temperature and polishing time are not particularly limited, but the polishing conditions are selected so that the surface layer region having a depth of 500 nm or more from the substrate surface becomes porous.
  • a Co-based alloy with a lamellar structure is immersed in a polishing solution as an anode, and either ⁇ phase or ⁇ phase is selectively removed by electrochemical reaction.
  • a polishing solution as an anode
  • materials with excellent corrosion resistance such as stainless steel and platinum are used.
  • the electrolysis conditions are not subject to any particular restrictions, but it is preferable to determine the voltage, current, polishing temperature, polishing time, etc. so that the surface layer depth of 500 nm or more from the surface of the substrate becomes porous.
  • ⁇ phase or ⁇ phase is selectively removed using the hardness difference of each phase.
  • the surface layer region porous from the substrate surface it is preferable to make the surface layer region porous from the substrate surface to a depth of 500 nm or more.
  • the depth of the porous surface layer can be adjusted as appropriate depending on the type, concentration, processing time, etc. of the processing solution used. If the depth does not reach 500 mn, sufficient effects due to the porous structure cannot be obtained, but if the depth is too deep, the effect corresponding to the polishing load cannot be obtained, so the maximum depth of the porous surface layer is about 800 ⁇ . Is preferred.
  • micropore size is less than ⁇ reflecting the lamellar structure layer spacing, The size is suitable for sustained release and familiarity with living bodies.
  • the lamellar structure is refined according to the solidification cooling conditions, the aging treatment conditions, the manufacturing history up to the aging treatment process, etc., the micropores become finer accordingly. Cold working after aging treatment is also an effective means for refining the lamellar structure.
  • the porous surface layer area is supported by a Co-based alloy with a lamellar structure, the inherent properties of the Co-based alloy such as high strength, wear resistance, and heat resistance are also utilized, and a porous structure that can provide various functions. Combined with the improved surface layer, it can be expected to be used in a wide range of applications such as various types of machinery, medical equipment, tools, catalyst carriers, and functional materials. For example, a drug-eluting stent that has recently started to be used in the medical field is applied to the stent and placed in the affected area, and the elution of the drug is continued for a certain period of time to prevent cell proliferation and eventually restenosis in the affected area. Yes.
  • a drug-mixed polymer is placed on the stent, and the surface of the stent is polymer coated to prevent drug diffusion.
  • drug elution sustained release control requires selection of drug density, polymer material, and the like.
  • the Co-base alloy with a porous surface layer allows the drug to be applied directly to the stent surface without the need for coating aids, increasing the amount of drug applied by the porous layer, and the sustained release derived from the surface shape. Sex control is also possible.
  • Co-Al binary alloys (Table 3) with A1 added in various proportions were melted and fabricated.
  • Test No. 7-9 the forged structure formed during the solidification and cooling process was kept.
  • Test Nos. 1 to 6 and 10 were hot-rolled and cold-rolled to a thickness of 1 mm, solutionized: 120 CTC x 15 minutes, aging: 600 ° C x 12 hours heat-treated into a lamellar structure did.
  • Each Co-Al alloy plate was observed with a microscope to investigate the precipitation state of the ⁇ ( ⁇ 2) phase.
  • SEM images of each Co-Al alloy plate were image-processed, and the volume ratio and layer spacing converted from the area ratio of the lamella structure were obtained.
  • the wear amount was measured SUJ-2 with in the mating member Ohkoshi type abrasion tester, the specific wear rate: 1 X 10- 6 mm 2 Roh kg the following ⁇ , (1.0 ⁇ 5.0) X 10- 6 the mm 2 / kg ⁇ , the (5.0 ⁇ 10) X 10- 6 mmVkg ⁇ , and evaluated wear resistance more than 10X 10- 6 mm 2 Zk g as X. .
  • the Co-Al alloys of Test Nos. 7 and 8 had a lamellar structure in which the ⁇ phase and ⁇ ( ⁇ 2) phase of the f.c c structure were repeated during the crystallization reaction during the solidification process.
  • test ⁇ .8 which has a slower cooling rate compared to test ⁇ .7, the layer spacing was widened.
  • Table 3 also shows the volume ratio and layer spacing converted from the area ratio of the lamellar structure obtained by image processing of the SEM image.
  • the mechanical strength and wear resistance of the Co-Al alloy also changed depending on the formation of the lamellar structure.
  • the Co-Al alloy with a lamellar structure formed on the entire surface had excellent wear resistance and high strength.
  • a Co-Al alloy with insufficient ⁇ ( ⁇ 2) phase precipitation is inferior in tensile strength and yield strength, while a Co-A1 alloy with a matrix of ⁇ ( ⁇ ⁇ 2) phase has poor elongation at break and lacks ductility. It was.
  • Table 3 Effects of content and properties on metal properties and physical properties
  • Density Electropolishing was performed by energizing at 30 A / dm 2 .
  • the Co-base alloy was pulled up from the polishing liquid and dried, and the surface of the Co-base alloy was observed with an SEM. As shown in Fig. 2 (b), a porous layer with microscopic cavities formed on the trace of the selectively eluted ⁇ ( ⁇ 2) phase was formed on the surface of the Co-based alloy.
  • porous layer is a unique phenomenon seen in the electropolishing of a Co-based alloy having a lamellar structure, and such a clear porous layer was not detected in tests No 1, 9 and 10 without a lamellar structure. It was.
  • the surface area of the electro-polished Co-based alloy was calculated by image analysis of an SEM image, and the surface area ratio was calculated as a ratio to the surface area of the Co-based alloy that was not electropolished.
  • the surface layer became porous and contained micropores, resulting in a significant increase in surface area.
  • the surface layer did not become porous after electropolishing.
  • Example 1 The Co-Al alloy of Test No. 5 in which a porous layer with a large surface area ratio was generated in Example 1
  • ⁇ ⁇ 2 phase
  • morphology of the porous layer we investigated the effect of solution treatment and aging temperature conditions on the layered precipitation of ⁇ ( ⁇ 2) phase and, consequently, the morphology of the porous layer.
  • the same electrolytic polishing as in Example 1 was employed.
  • solution precipitation temperature 900-1400 ° C
  • aging temperature 500-900 ° C promotes layered precipitation of ⁇ (3 ⁇ 42) phase
  • surface area ratio after electropolishing 5.9 or more
  • the porous layer was formed in the surface layer region having a depth of 5 ⁇ or more from the surface of the Co-based alloy.
  • ⁇ ( ⁇ 2) phase At an aging temperature of less than 500 ° C, the formation of ⁇ ( ⁇ 2) phase was insufficient and the lamellar structure was not formed, so that the surface of the Co-based alloy was not made porous after electropolishing.
  • the aging temperature exceeds 900 ° C, the ⁇ ( ⁇ 2) phase does not precipitate in layers, and the electropolished Co-based alloy has a surface area ratio of 1.2 from the surface to depth: lOOnm, which is not enough to provide the necessary functions.
  • the porous structure was sufficient.
  • the precipitate was aged without being sufficiently dissolved, so the formation of lamellar structure was inhibited by the residue of the precipitate, and the electro-polished Co-based alloy The surface was roughened without becoming porous.
  • solution treatment was performed at a high temperature exceeding 1400 ° C, a massive precipitate derived from the liquid phase generated by partial melting was generated, and the surface state was not suitable for porous formation. . ,
  • Table 5 Effect of the grinding conditions on the shape of Co-6.9 *% A1 alloy metal fiber, and 3 ⁇ 4 surface of the LK surface layer
  • HC1 H 2 O 10g: 25ml: Electropolishing scissors using 100ml were adopted.
  • stainless steel was used for the cathode, the liquid temperature was set to 25 ° C, the current density was set to 30AZdm 2 , and the immersion time was set to 15 minutes.
  • the surface area ratio was 1.5 or more.
  • a porous surface layer region is formed by selective removal of the ⁇ phase, a porous skeleton is formed by the remaining ⁇ phase, so the porous layer region is soft and ductile, the pore size is small, and the depth of the porous layer is small. There was a tendency to increase.
  • a Co-6.9% Al alloy having a lamellar structure by the same aging treatment as in Example 3 was physically polished, and the ⁇ phase was selectively removed from the Co-based alloy surface layer.
  • a lamellar structure was formed by solution treatment of the Co-base alloys shown in Tables 8 and 9 at 1200 ° CX for 15 minutes, followed by aging treatment at 600 ° CX for 24 hours.
  • Passive holding current density is 0 05A / m 2 or less ⁇ , 0.05 ⁇ 0 lAZm 2 ⁇ , 0 l ⁇ 0.3A / m 2 ⁇ , (AZm 2 or more Corrosion resistance was evaluated with X as X.
  • Table 8 Effect of the third component ⁇ 3 ⁇ 4 ⁇ on lamellar controversy, surface area, corrosion resistance (Solution: 1200 ⁇ 15 ⁇ ⁇ Aging: 600 ⁇ 24 o'clock)
  • ⁇ phase or ⁇ ( ⁇ 2) phase from the surface layer of Co-Al alloy with lamellar structure and making it porous, substance retention ability, sustained release, strong bonding Functions such as sexuality, biocompatibility, heat dissipation, and catalytic activity are added.
  • the excellent corrosion resistance inherent in the Co alloy, the high strength and wear resistance resulting from the lamellar tissue are also utilized, so that medical materials such as drug-eluting stents and catheters, biomaterials such as artificial bones and artificial roots It is useful as a catalyst carrier, selective adsorption bed, heat sink bearing and so on.

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

Cette invention concerne un alliage à base de Co comprenant une composition fondamentale de système binaire Co-Al contenant de 3 à 15 % d'Al et présentant une structure lamellaire dans laquelle la phase α et la phase β (B2) de la structure f.c.c. sont superposées en couches. L'alliage à base de Co est modifié de façon qu'il comporte une zone à couche de surface poreuse efficace en termes de capacité de retenue chimique, de libération soutenue, de biocompatibilité, etc. par élimination sélective de la phase α ou de la phase β de la couche de surface. Comme troisième composant, au moins un élément sélectionné parmi Ni, Fe, Mn, Ga, Cr, V, Ti, Mo, Nb, Zr, W, Ta, Hf, Si, Rh, Pd, Ir, Pt, Au, B, C et P peut être utilisé en une quantité totale comprise entre 0,001 et 60 %.
PCT/JP2006/320689 2005-10-11 2006-10-11 Element fonctionnel en alliage a base de co et procede de production de cet alliage WO2007043688A1 (fr)

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US12/098,771 US8021499B2 (en) 2005-10-11 2008-04-07 Functional member from co-based alloy and process for producing the same

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WO2023027012A1 (fr) * 2021-08-26 2023-03-02 国立研究開発法人物質・材料研究機構 Élément en alliage de cobalt et de chrome, son procédé de production et dispositif l'utilisant

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JP2012246513A (ja) * 2011-05-25 2012-12-13 Kaneka Corp ステント研磨装置
JP2019516012A (ja) * 2016-04-20 2019-06-13 アーコニック インコーポレイテッドＡｒｃｏｎｉｃ Ｉｎｃ． アルミニウム、コバルト、クロム、及びニッケルのｆｃｃ材料、ならびにそれから作製される製品
WO2023027012A1 (fr) * 2021-08-26 2023-03-02 国立研究開発法人物質・材料研究機構 Élément en alliage de cobalt et de chrome, son procédé de production et dispositif l'utilisant

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US8021499B2 (en) 2011-09-20
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EP1935997A1 (fr) 2008-06-25
CN100582272C (zh) 2010-01-20
KR100991906B1 (ko) 2010-11-04
CN101287849A (zh) 2008-10-15
KR20080058357A (ko) 2008-06-25
EP1935997B1 (fr) 2012-10-03
WO2007043688A9 (fr) 2007-06-07
EP1935997A4 (fr) 2009-12-09

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